TW201623511A - Protection of new electro-conductors based on nano-sized metals using direct bonding with optically clear adhesives - Google Patents

Abstract

The present invention is an adhesive composition for stabilizing an electrical conductor. The adhesive composition includes a base polymer and an additive to interfere with photo-oxidation of metals. When the adhesive composition is in contact with the electrical conductor, the electrical conductor has less than about a 20% change in electrical resistance over a period of about 500 hours of light exposure.

Description

Direct bonding with optical clear adhesive to protect new electrical conductors based on nano-sized metals

This invention relates to an optically clear adhesive composition. In particular, the present invention relates to optical clear adhesive compositions that stabilize electrical conductors.

In the past several decades, transparent conductive films have been widely used in applications such as touch panel displays, liquid crystal displays, electroluminescent illumination, organic light emitting diode devices, and photovoltaic solar cells. A transparent conductive film based on indium tin oxide (ITO) is the most suitable choice for applications. However, ITO-based transparent conductive films are limited by the high cost, the need for complex and expensive equipment and processes, the relative (higher contrast metal) resistance, and the tendency to have brittleness and chipping; When deposited on a flexible substrate. In recent years, new conductors based on metal nanoparticles, nanorods, and nanowires have made significant advances in technology, with printed patterns, random patterns (to minimize visibility and ripple), and (from The metal mesh of nano-sized metal materials has become much more attractive to the electronics industry. Metal conductors based on silver and copper are probably the most common. A specific example is Yinnai. Silver nanowires (SNWs). The SNW-based film imparts high conductivity, high light transmission, superior flexibility and ductility at a moderate cost, making it a desirable alternative to ITO in many applications; Thin and more flexible devices.

However, the challenge of keeping SNW stable for long periods of time is very high because it is sensitive to light and ambient exposure. One such example is the decomposition of the conductive track of the SNW base touch panel at the viewing area of the display and/or near the ink edge (black or white ink edge around the display) due to UV. This decomposition can result in a sudden loss in conductivity and, therefore, the function of the touch panel, possibly due to oxidation of the light of the SNW. Some literature indicates that silver's so-called plasmonic resonance can promote silver oxidation of silver oxide.

In one embodiment, the invention is an adhesive composition for stabilizing an electrical conductor. The adhesive composition includes a base polymer and an additive for interfering with photooxidation of the metal. When the electrical conductor is coated with the adhesive composition, the electrical resistance of the electrical conductor has a change of less than about 20% during one exposure of about 500 hours.

In another embodiment, the invention is a method for stabilizing an electrical conductor. The method includes providing an adhesive composition and applying the adhesive composition to the electrical conductor. The adhesive composition includes a base polymer and an additive to interfere with or prevent oxidation of the electrical conductor. When the electrical conductor is coated with the adhesive composition, the electrical resistance of the electrical conductor has a change of less than about 20% during one exposure of about 500 hours.

100‧‧‧Test materials

102‧‧‧Silver nanowire; SNW coating

104‧‧‧ polyester film; PET film

106‧‧‧Optical clear adhesive strip; OCA strip

108‧‧‧Microscope slides; slides

110‧‧‧Black insulating tape; black tape

Figure 1A is a top plan view of a construction sample used to measure the change in electrical resistance of a silver nanowire film.

Figure 1B is a side elevational view of the construction sample of Figure 1A for measuring the change in electrical resistance of a silver nanowire film.

These figures are not drawn to scale and are intended for purposes of illustration only.

The present invention is an optical clear adhesive (OCA) composition that provides stability to nanowire sensors in a variety of situations, even without ultraviolet (UV) or visible light protective coatings. The optical clear adhesive composition comprises a base polymer and an additive that interferes with photooxidation of the metal. The base polymer can be selected from any optical clear adhesive polymer. Examples of suitable adhesives include antioxidants, metal complexing agents, reducing agents, materials that are both reducible and miscible metals, and combinations thereof. The OCA of the present invention can be based on metal nanoparticles, nanorods, and nanowires for, for example, touch screens, electromagnetic shielding, photovoltaic panels, metal mesh, transparent heating line patterns of windows, etc. to stabilize electrical conductors. When exposed to UV and visible light, these metal conductors can be easily decomposed, resulting in loss of electrical conductivity. By applying the OCA of the present invention directly to the conductor, expensive protective coatings (i.e., barriers, UV blocking) can be avoided and the assembly process of the article can be simplified. The invention also encompasses methods of use and articles containing such OCA in contact with the metallic conductors.

The nature of the optical clear adhesive composition of the present invention may be pressure sensitive or heat activated. Similarly, they can be applied as a film adhesive, directly as a hot melt dispensing, or as a liquid OCA application and as a final assembly.

The adhesive composition of the present invention comprises a base polymer. Although an adhesive composition derived from an acrylic base polymer (especially a random (meth)acrylic copolymer) is preferred for its moderate cost and wide availability, other polymerizations may be used. The material acts as an adhesive composition without departing from the intended scope of the invention. Examples of other polymers include, but are not limited to, polyesters, polyurethanes, polyureas, polyamines, polyoxyxides, polyolefins, acrylic block copolymers, rubber block copolymers. (ie, polystyrene-polyisoprene-polystyrene (SIS), polystyrene-poly(ethylene butene)-polystyrene (SEBS), polystyrene-poly(ethylene propylene)-polyphenylene Ethylene (SEPS), etc., and combinations thereof. Mixtures of these polymers, including such (meth) acrylates, can also be used in obtaining optical clear blends.

The polymers may be commercially available or may be polymerized by conventional means including solution polymerization, thermal bulk polymerization, addition polymerization, ring opening polymerization, emulsion polymerization, UV or visible light. The overall polymerization method and the condensation polymerization method are triggered.

The adhesive composition of the present invention also includes at least one additive that interferes with photooxidation. These additives act to interfere with or prevent oxidation of the metal conductor upon exposure to UV light. Suitable additives are therefore those which interfere with the photooxidation of the metal. Examples of suitable additives that interfere with metal photooxidation include, but are not limited to, metal miscible materials, antioxidants, reducing agents, metal mismatching and reducing materials, and combinations thereof.

Metal Misc. This material can migrate to the surface of the metal conductor and form a complex with the surface that bonds the agent to the surface. Without being bound by theory, it is believed that in doing so, the additive prevents moisture and oxygen from entering the metal surface, reducing or eliminating the risk of dissolving any oxide species. Examples of suitable complexing agents include but It is not limited to a carboxylic acid (for example, hydrogenated cinnamic acid or citrate). Natural compounds such as ascorbic acid can also be used as long as they are soluble in the adhesive interstitial.

The antioxidant acts to interfere with the photochemical initiation of the decomposition reaction and thus inhibits oxidation of the electrical conductor. While antioxidants are known to interfere with the oxidation process, their use in conjunction with readily oxidizable metal conductors (e.g., nanoparticles, nanorods, or nanowires) has not been previously known in the prior art. Examples of suitable antioxidants are those sold under the trade name Irganox (i.e., Irganox 1010, Irganox 1024, and Irganox 1076) available from BASF, Florham Park, New Jersey, or Cyanox, available from Woodland Park. CYTEC, New Jersey. Natural antioxidants such as ascorbic acid can also be used as long as they are soluble in the adhesive interstitial.

The reducing agent can interfere with the oxidation of the metal conductor in at least two ways. The reducing agent can react with an oxygen species that oxidizes the metal to a metal oxide and/or the like can quickly reduce the metal oxide to a metallic state, allowing the metal to be preserved and the metal oxide to be insoluble and removed from the metal In addition, the conductivity is maintained. Without being bound by theory, it is believed that in some cases, these compounds are preferably adsorbed onto the metal surface such that they may be more effective than the reducing agent. Additional examples of suitable reducing agents include compounds which are organic molecules having a relatively low oxidation potential, such as phosphines and unsaturated and polyunsaturated acids and the like. Examples include, but are not limited to, linseed oleic acid, oleic acid, linoleic acid, cinnamic acid, cinnamyl alcohol, vanillyl alcohol, citronellol, citronellal, citral, and cinnamaldehyde. Terpenes such as a pinene and limonene can be used. Unsaturated rosin acids and abietic acids (such as rosin acid) can also be used. In some cases, the reducing agent can be copolymerized. One example of a suitable copolymerization additive is citronellyl acrylate.

The metal mismatch and reduction material acts as a metal miscible material and a reducing agent, as described above. The compound having a carboxylic acid group may be one of such materials, and is suitably used in the adhesive composition of the present invention. Examples of suitable metal miscible and reducing materials include, but are not limited to, unsaturated and polyunsaturated acids such as linoleic acid, oleic acid, linoleic acid, and cinnamic acid.

The minimum amount of additive required in the adhesive composition will depend on the environmental exposure and the amount of electrical resistance that will be tolerated. In one embodiment, the additives are present in the adhesive composition in an amount of about 5% by weight or less of the dry adhesive coating. In one embodiment, the additives are present in the adhesive composition at a level of at least about 0.1% by weight. In one embodiment, the additives are present in the adhesive composition at between about 0.5 and about 3 weight percent.

This additive significantly improves the stability of the conductor when it comes into contact with optically clear adhesives, even under fairly intense light. Stability is determined by the change in resistance over a specified period of time. Without being bound by theory, it is generally believed that stabilization can interfere with the process of photooxidation. In one embodiment, the electrical resistance of the electrical conductor of the adhesive composition of the present invention is coated or laminated for a period of about three weeks (500 hours), and the electrical resistance will have a change of less than about 20%, specifically less than about 10% and more specifically less than about 5%.

Since the adhesive composition must be optically clear, the additives should be miscible in the adhesive interstitial to have minimal or no effect on the optical properties of the adhesive composition. The final formulation retains its optical clarity. "Optically clear" means having a high visible light transmission of at least about 90%, a haze of no more than about 2%, and also a neutral color and no whiteness. Non-whitening. However, in some cases (such as diffusing adhesives), the optical requirements may be less stringent. Although the adhesive composition is primarily described as an optical clear adhesive throughout the specification, the same additives may be used, for example, in direct contact with the photoresist of a metal conductor, or as a dispersion of nanosized metal particles themselves. Part of it, for example, silver nanowire ink.

These additives must also not affect the mechanical durability of the display assembly using the adhesive composition. In one embodiment, the adhesive composition has a 180 degree peel force after a dwell time of 20 minutes or 72 hours of at least about 30 oz/吋, specifically more than at least about 40 oz. /吋 and more specifically at least about 50 oz/吋. These additives should also be soluble in the adhesive interstitial.

Depending on the process used to make the adhesive composition, the additives may also be compatible with the polymerization, coating, and curing procedures used to produce the adhesive composition. For example, there must be no significant blockage or interference with the UV polymerization or curing process. In some embodiments, the additives must also be non-volatile in a solvent or hot melt coating procedure.

In one embodiment, to improve environmental durability, the adhesive composition also includes a crosslinking agent. The polymers of the adhesive composition can be crosslinked by methods well known in the art including, for example, physical crosslinking (e.g., high Tg graft or block, hard segment, small). Microcrystalline, etc.), ionic crosslinking (eg, carboxylic acid cross-linking with a metal ion or acid/base type), and covalent cross-linking (eg, polyfunctional aziridine with carboxylic acid, melamine, and carboxylic acid, Copolymerization of polyfunctional (meth) acrylate For cooperation, and for example, a hydrogen abstraction mechanism with a benzophenone or a hydrazine compound.

The present invention addresses the need for a rapid emergence to protect new electrical conductors derived from nano-sized metals such as silver and copper. The combination of a base polymer and an additive that interferes with the photooxidation of the metal not only provides environmental protection for these conductors, but is also largely compatible with UV curing procedures, including some photoresists for liquid OCA, patterns that can be used for conductors. And a one-web polymerization process for producing OCA.

Instance

The invention is described in more detail in the following examples, which are intended to be illustrative only, as many variations and modifications within the scope of the invention will be apparent to those skilled in the art. All parts, percentages, and ratios recited in the examples below are by weight unless otherwise indicated.

Materials: The materials used were taken from the following suppliers.

Preparation of test samples

1A and 1B respectively show a plan view and a side view of the test sample 100, which show an example of a structure for measuring the change in the resistance of the silver nanowire film. Silver nanowire 102 (SNW) was made by coating silver ink (Cambrios Technologies Corporation, Sunnyvale, CA) on polyester (PET) film 104. The resistance of the coated sheet is typically about 50 ohms/sq. The release liner is removed from one side of a 2 inch by 3 inch optical clearing adhesive (OCA) strip 106 and placed in direct contact with the side of the PET film 104 coated with the silver nanowire 102. The OCA strip 106 was rolled four times with a small rubber hand roll to ensure that no air bubbles were embedded between the OCA 106 and the SNW coating 102. The second liner was removed from the OCA and the OCA/silver nanowire film assembly was laminated to a 2 inch by 3 inch microscope slide 108. As shown in Figure 1, half of the slides 108 opposite the OCA/silver nanowire film assembly are covered by a black insulating tape 110 while the other half remains open. The test sample 100 is irradiated from the side of the cover tape with a xenon arc lamp to allow light to pass through the glass or be blocked by the black tape 110.

method Method for measuring resistance change of silver nanowire film

Resistance changes were measured in three different zones of the test strip using a Delcom 707 Conductivity Monitor (Delcom Instruments, Inc., Minneapolis, MN), and the results are summarized in Tables 1 through 5. In Tables 1 to 5, the measurement of the silver nanowire completely covered by the black insulating tape is referred to as "no light", and the measurement of the silver nanowire partially covered by the black insulating tape is referred to as "interface", and The measurement of the silver nanowires that are completely exposed to the xenon arc lamp is referred to as "light". Each circle is measured at least twice. If measured Different, this information will generally be excluded and a new sample will be tested. It is believed that a resistance change of less than 25% after 500 hours of exposure is acceptable performance. The "matte" measurement was performed with an internal control to ensure that there was no adverse interaction between the OCA film and the silver nanowire in the absence of xenon arc exposure. A resistance change greater than 25% in any of the "no light", "interface" or "light" measurement areas is considered a failure of the test material. Blank spaces in the table indicate that no data has been collected.

The percent resistance change for the exposure time of the xenon arc lamp is calculated as follows: % resistance change = 1 / (100 * (G _{t -} G ₀ ) / G ₀ ), where G ₀ has no initial conductivity of xenon arc exposure, The G _t is the conductivity after the exposure of the xenon arc lamp for t hours. The parameters of the xenon arc exposure are as follows:

The parameters of the X-ray lamp exposure condition A are: illuminance at 340 nm of 0.4 W/m ² , black panel temperature of 60 ° C, temperature of 38 ° C, and relative humidity of 50%.

The parameters of the X-ray lamp exposure condition B are: for the first 300 hours, the sample was exposed to the following conditions: illuminance at 340 nm 0.4 W/m ² , black plate temperature 60 ° C, after which the sample was additionally exposed to the following conditions: The illuminance at 340 nm was 0.55 W/m ² , the temperature at the black disk was 70 ° C, the temperature was 47 ° C, and the relative humidity was 50%.

Method of measuring haze

Haze was measured according to ASTM D 1003 92. The results of Adhesive Example 13 are summarized in Table 6. The samples were prepared by cleaning the LCD glass three times with isopropyl alcohol and completely drying it with KIMWIPES (Kimberly-Clark Corp., Neenah, WI). Each OCA film is cut to a size sufficient to cover the entrance pupil of the sphere. Move the release liner from one side In addition, the OCA film was laminated four times on a small rubber manual roll onto the LCD glass. The sample was inspected to ensure that it has no visible internal voids, particles, scratches, and flaws. The second liner was removed prior to the haze test. Haze was measured against the background of the LCD glass using an UltraScan Pro spectrophotometer (Hunter Associates Laboratory, Inc., Reston, VA).

Method of chromaticity measurement

The color is measured according to ASTM E1164 07/CIELAB. The results of Adhesive Example 13 are summarized in Table 6. The samples were prepared by cleaning the LCD glass three times with isopropyl alcohol and completely drying it with KIMWIPES (Kimberly-Clark Corp., Neenah, WI). Each OCA film is cut to a size sufficient to cover the entrance pupil of the sphere. The release liner was removed from one side and the OCA film was laminated to the LCD glass with a four-times small rubber hand roller. The sample was inspected to ensure that it has no visible internal voids, particles, scratches, and flaws. The second liner was removed prior to the color test. The chromaticity was measured against the background of the LCD glass using an UltraScan Pro spectrophotometer (Hunter Associates Laboratory, Inc., Reston, VA).

Durability and anti-whitening method

Remove the release liner from a 2 inch by 3 inch OCA strip and apply the strip to a 5 mil thick primer poly(ethylene terephthalate) (PET) film (Skyrol SH81, SKC Inc) ). The OCA strip was rolled four times with a small rubber hand roller to ensure that no air bubbles were buried. Removing the second liner from the OCA strip and laminating the OCA strip to a 2 fold 3 inch LCD glass or 5 mil thick primer PET film. The OCA strip was rolled four times with a small rubber hand roller to ensure that no air bubbles were buried. The samples were placed in a test chamber at 65 ° C and 90% relative humidity, and the appearance of bubbles or whitening was observed every other day. The formation of bubbles indicates insufficient durability of the sample. In terms of anti-whitening, a sample with visible whitening is removed from the test chamber, and if whitening disappears within 3 minutes after removal, it is considered to pass. The results of Adhesive Example 13 are summarized in Table 6.

180 degree peel force adhesion measurement method

Modified ASTM D903-98, 180 degree peel, 12 吋 / min. The floating glass was cleaned three times with isopropanol and completely dried with KIMWIPES. An OCA sample was cut to a size of 1 inch wide by about 12 inches long. The release liner was removed from one side and the OCA was rolled four times back to a 2 mil prime PET film with a small rubber hand roller to ensure no embedding of air bubbles. The second liner was removed and the OCA was rolled three times back to the floating glass with a 5 lb hand roller to ensure no embedding bubbles. After 12 minutes or 72 hours of stand-by time at room temperature (as indicated in Table 6), the IMASS SP-2000 Slide/Peel Tester (IMASS, Inc, Accord, MA) was used to measure at 12 吋/min. 180 degree peel adhesion.

Formulation Acrylic copolymer 1

A mixture of 2-EHA/iBOA/HEA=55/25/20 (parts by mass) was prepared, and the mixture was diluted with ethyl acetate/toluene (1:1) to obtain a 50% by mass. Monomer concentration. Vazo-52 was then added as a starter at a ratio of 0.15 mass% based on the mass of the monomer. The mixture was poured into a glass vial and flushed with nitrogen for 10 minutes and then sealed and stored in an inert atmosphere. Subsequently, the reaction was allowed to proceed in a constant temperature bath at 55 ° C for 6 hours. The reaction temperature was then increased to 75 ° C for an additional 4 hours. A clear viscous solution is obtained. This acrylic copolymer solution was used in the following examples without isolating the copolymer. The resulting acrylic copolymer had a weight average molecular weight of 563,000 g/mol, which was measured by gel permeation chromatography on polystyrene standards.

Comparative example 1

For the acrylic copolymer 1, KBM 403 and Desmodur N3300 were added at a ratio of 0.05 and 0.4 parts by mass, respectively, based on the mass of the dried copolymer. Next, the prepared solution was coated on a 50 μm thick RF22N release film and dried in an oven at 70 ° C for 30 minutes. After drying, the PSA had a thickness of 50 μm. Next, the PSA surface was laminated with a 50 μm thick RF02N release film and stored at 65 ° C for 24 hours.

Comparative example 2

A monomer premix was prepared using Darocur 1173 (0.02 parts), EHA (55 parts), iBOA (25 parts), and HEA (20 parts). The mixture was partially polymerized by exposure to ultraviolet radiation in a nitrogen-rich atmosphere to provide a coatable slurry having a viscosity of about 1000 cps (1 PaS). Next, HDDA (0.15 parts), KBM-403 (0.05 parts), and Irgacure 651 (0.15 parts) were added to 100 parts of the slurry. After mixing, the slurry was knife-coated with a thickness of 50 μm between two polyfluorinated release liners (RF02N/RF12N). The resulting coated material is then exposed to a low intensity ultraviolet radiation source having a spectral output of one of 300 to 400 nm at a total UVA dose of about ² J/cm ² and a maximum intensity of 351 nm.

Adhesive example 1

To the acrylic copolymer 1, ethyl decyl tri-2-ethylhexyl, KBM 403 and Desmodur N3300 were added in a ratio of 5, 0.05 and 0.4 parts by mass, respectively, based on the mass of the copolymer. Next, the prepared solution was coated on a 50 μm thick RF22N release film and dried in an oven at 70 ° C for 30 minutes. After drying, the PSA had a thickness of 50 μm. Next, the PSA surface was laminated with a 50 μm thick RF02N release film and aged at 65° for 24 hours.

Adhesive example 2

To the acrylic copolymer 1, biphenylphosphine, KBM 403 and Desmodur N3300 were added at a ratio of 5, 0.05 and 0.4 parts by mass, respectively, based on the mass of the dried copolymer. Next, the prepared solution was coated on a 50 μm thick RF22N release film and dried in an oven at 70 ° C for 30 minutes. After drying, the PSA had a thickness of 50 μm. Next, the PSA surface was laminated with a 50 μm thick RF02N release film and aged at 65° for 24 hours.

Adhesive Example 3

To the acrylic copolymer 1, hydrogen cinnamic acid, KBM 403 and Desmodur N3300 were added at a ratio of 5, 0.05 and 0.4 parts by mass, respectively, based on the mass of the dried copolymer. Next, the prepared solution was coated on a 50 μm thick RF22N release film and dried in an oven at 70 ° C for 30 minutes. After drying, the PSA had a thickness of 50 μm. Next, the PSA surface was laminated with a 50 μm thick RF02N release film and aged at 65° for 24 hours.

Adhesive example 4

To the acrylic copolymer 1, Irganox 1076, KBM 403 and Desmodur N3300 were added at a ratio of 1, 0.05 and 0.4 parts by mass, respectively, based on the mass of the copolymer. Next, the prepared solution was coated on a 50 μm thick RF22N release film and dried in an oven at 70 ° C for 30 minutes. After drying, the PSA had a thickness of 50 μm. Next, the PSA surface was laminated with a 50 μm thick RF02N release film and aged at 65° for 24 hours.

Adhesive example 5

To the acrylic copolymer 1, Irganox 1024, KBM 403 and Desmodur N3300 were added at a ratio of 1, 0.05 and 0.4 parts by mass, respectively, based on the mass of the copolymer. Next, the prepared solution was coated on a 50 μm thick RF22N release film and dried in an oven at 70 ° C for 30 minutes. After drying, the PSA had a thickness of 50 μm. Next, the PSA surface was laminated with a 50 μm thick RF02N release film and aged at 65° for 24 hours.

Adhesive Example 6

To the acrylic copolymer 1, lemon olein, KBM 403 and Desmodur N3300 were added at a ratio of 5, 0.05 and 0.4 parts by mass, respectively, based on the mass of the copolymer. Next, the prepared solution was coated on a 50 μm thick RF22N release film and dried in an oven at 70 ° C for 30 minutes. After drying, the PSA had a thickness of 50 μm. Next, the PSA surface was laminated with a 50 μm thick RF02N release film and aged at 65° for 24 hours.

Adhesive Example 7

To the acrylic copolymer 1, β-monoolefin, KBM 403 and Desmodur N3300 were added in a ratio of 5, 0.05 and 0.4 parts by mass, respectively, based on the mass of the copolymer. Next, the prepared solution was coated on a 50 μm thick RF22N release film and dried in an oven at 70 ° C for 30 minutes. After drying, the PSA had a thickness of 50 μm. Next, the PSA surface was laminated with a 50 μm thick RF02N release film and aged at 65° for 24 hours.

Adhesive Example 8

To the acrylic copolymer 1, cinnamyl alcohol, KBM 403 and Desmodur N3300 were added at a ratio of 5, 0.05 and 0.4 parts by mass, respectively, based on the mass of the copolymer. Next, the prepared solution was coated on a 50 μm thick RF22N release film and dried in an oven at 70 ° C for 30 minutes. After drying, the thickness of the PSA is 50 Mm. Next, the PSA surface was laminated with a 50 μm thick RF02N release film and aged at 65° for 24 hours.

Adhesive Example 9

To the acrylic copolymer 1, cinnamaldehyde, KBM 403 and Desmodur N3300 were added in a ratio of 5, 0.05 and 0.4 parts by mass, respectively, based on the mass of the copolymer. Next, the prepared solution was coated on a 50 μm thick RF22N release film and dried in an oven at 70 ° C for 30 minutes. After drying, the PSA had a thickness of 50 μm. Next, the PSA surface was laminated with a 50 μm thick RF02N release film and aged at 65° for 24 hours.

Adhesive Example 10

To the acrylic copolymer 1, cinnamic acid, KBM 403 and Desmodur N3300 were added in a ratio of 5, 0.05 and 0.4 parts by mass, respectively, based on the mass of the copolymer. Next, the prepared solution was coated on a 50 μm thick RF22N release film and dried in an oven at 70 ° C for 30 minutes. After drying, the PSA had a thickness of 50 μm. Next, the PSA surface was laminated with a 50 μm thick RF02N release film and aged at 65° for 24 hours.

Adhesive Example 11

To the acrylic copolymer 1, based on the mass of the copolymer, adding linolenic acid, KBM 403 and 5, 0.05 and 0.4 parts by mass, respectively. Desmodur N3300. Next, the prepared solution was coated on a 50 μm thick RF22N release film and dried in an oven at 70 ° C for 30 minutes. After drying, the PSA had a thickness of 50 μm. Next, the PSA surface was laminated with a 50 μm thick RF02N release film and aged at 65° for 24 hours.

Adhesive Example 12

To the acrylic copolymer 1, rosin acid, KBM 403 and Desmodur N3300 were added at a ratio of 5, 0.05 and 0.4 parts by mass, respectively, based on the mass of the copolymer. Next, the prepared solution was coated on a 50 μm thick RF22N release film and dried in an oven at 70 ° C for 30 minutes. After drying, the PSA had a thickness of 50 μm. Next, the PSA surface was laminated with a 50 μm thick RF02N release film and aged at 65° for 24 hours.

Adhesive Example 13

A monomer premix was prepared using Darocur 1173 (0.02 parts), EHA (55 parts), iBOA (25 parts), and HEA (20 parts). The mixture was partially polymerized by exposure to ultraviolet radiation in a nitrogen-rich atmosphere to provide a coatable slurry having a viscosity of about 1000 cps (1 PaS). Next, HDDA (0.15 parts), KBM-403 (0.05 parts), Irganox 1024 (1 part), and Irgacure 651 (0.15 parts) were added to 100 parts of the slurry, and after mixing, it was used in a thickness of 50 μm. The knife was coated between two polyfluorinated release liners (RF02N/RF12N). The resulting coated material is then exposed to a low intensity ultraviolet radiation source having a spectral output of one of 300 to 400 nm at a total UVA dose of about 2 J/cm ² and a maximum intensity of 351 nm.

Adhesive Example 14

A mixture of β-citronellol (300.00 g, 1.92 mol), hexane (1500 mL), and triethylamine (212.49 g, 2.10 mol) was cooled in an ice bath. Propylene hydrazine chloride (190.08 g, 2.10 mol) was added dropwise over 5 hours. The mixture was stirred at room temperature for 17 hours and then filtered. The solution was concentrated under vacuum and then washed with water. The solvent was removed under vacuum to provide a crude oil that was purified by vacuum distillation. A colorless oil (citronellyl acrylate 282.83 g) was collected at 0.30 mmHg at 70 to 75 °C.

A monomer premix was prepared using Darocur 1173 (0.02 parts), EHA (55 parts), iBOA (25 parts), and HEA (20 parts). The mixture was partially polymerized by exposure to ultraviolet radiation in a nitrogen-rich atmosphere to provide a coatable slurry having a viscosity of about 1000 cps (1 PaS). Next, HDDA (0.15 parts), KBM-403 (0.05 parts), citronella acrylate (2 parts), and Irgacure 651 (0.15 parts) were added to 100 parts of the slurry, and after mixing, they were 50 μm. The thickness was applied by knife to two polyoxygenated release liners (RF02N/RF12N). The resulting coated material is then exposed to a low intensity ultraviolet radiation source having a spectral output of one of 300 to 400 nm at a total UVA dose of about ² J/cm ² and a maximum intensity of 351 nm.

Table 1: Stabilizers for stabilizing silver nanowires

Although the present invention has been described with reference to the preferred embodiments thereof, those skilled in the art can understand that the form and details can be changed without departing from the spirit and scope of the invention.

100‧‧‧Test materials

102‧‧‧Silver nanowire; SNW coating

108‧‧‧Microscope slides; slides

110‧‧‧Black insulating tape; black tape

Claims (20)

An adhesive composition for stabilizing an electrical conductor, the adhesive composition comprising: a base polymer; and an additive for interfering with photooxidation of the metal; wherein the electrical conductor contacts the adhesive composition The electrical conductor has a resistance of less than about 20% change during one exposure period of about 500 hours. The adhesive composition of claim 1, wherein the additive is selected from the group consisting of a metal miscible material, an antioxidant, a reducing agent, a metal mismatch and a reducing material, and combinations thereof. The adhesive composition of claim 1, wherein the additive comprises up to about 5% by weight of the adhesive composition. The adhesive composition of claim 1, wherein the additive comprises at least about 0.1% by weight of the adhesive composition. The adhesive composition of claim 1, wherein the additive comprises between about 0.5 and about 3% by weight of the adhesive composition. The adhesive composition of claim 1, wherein the base polymer comprises one of the following: polyester, polyurethane, polyurea, polyamine, polyoxyn, polyene, acrylic block copolymer (acrylic block copolymer), rubber block copolymer or random (meth)acrylic copolymer. The adhesive composition of claim 6, wherein the base polymer is a random (meth)acrylic copolymer. The adhesive composition of claim 1, wherein the electrically conductive system is based on a metallic conductor. The adhesive composition of claim 8, wherein the metal conductors comprise silver or copper. The adhesive composition of claim 8, wherein the metal conducting system is a metal nanoparticle, a nanorod, and a nanowire. The adhesive composition of claim 1, which further comprises a crosslinking agent. The adhesive composition of claim 1, wherein when the electrical conductor is coated with the adhesive composition, the electrical resistance of the electrical conductor has a change of less than about 10% during one exposure period of about 500 hours. A method for stabilizing an electrical conductor, the method comprising: providing an adhesive composition comprising: a base polymer; and an additive for interfering with or preventing oxidation of the electrical conductor; and the adhesive The composition is coated or laminated to the electrical conductor; wherein when the electrical conductor is coated with the adhesive composition, the electrical conductor has a resistance of less than about 20% change during one exposure period of about 500 hours. The method of claim 13, wherein the additive is selected from the group consisting of a metal miscible material, an antioxidant, a reducing agent, a metal mismatch and a reducing material, and combinations thereof. The method of claim 13 wherein the additive comprises between about 0.1 and about 5% by weight of the adhesive composition. The method of claim 13, wherein the base polymer comprises one of the following: polyester, polyurethane, polyurea, polyamine, polyoxyn, polyene, acrylic block copolymer, rubber embedded Segment copolymer or random (meth)acrylic copolymer. The method of claim 13, wherein the conductivity system is based on a metal conductor. The method of claim 17, wherein the metal conducting system is a metal nanoparticle, a nanorod, and a nanowire. The method of claim 13 further comprising a crosslinking agent. The method of claim 13, wherein the electrical conductor has a resistance of less than about 10% change during one exposure period of about 500 hours when the adhesive composition is coated or laminated to the electrical conductor.